TY - JOUR
T1 - Studies on the mechanism of action of prekinamycin, a member of the diazoparaquinone family of natural products
T2 - Evidence for both sp2 radical and orthoquinonemethide intermediates
AU - Feldman, Ken S.
AU - Eastman, Kyle J.
PY - 2006/9/27
Y1 - 2006/9/27
N2 - The putative reductive activation chemistry of the diazoparaquinone antibiotics was modeled with Bu3Sn-H and prekinamycin dimethyl ether along with prekinamycin itself. Reaction in various combinations of aromatic solvents, with and without the nucleophile benzylmercaptan present, led to isolation of both radical-trapping arene adducts and nucleophilic capture benzyl thioether products. On the basis of these product distribution studies, the intermediacies of, first, a cyclopentenyl radical and, next, an orthoquinonemethide electrophile are postulated.
AB - The putative reductive activation chemistry of the diazoparaquinone antibiotics was modeled with Bu3Sn-H and prekinamycin dimethyl ether along with prekinamycin itself. Reaction in various combinations of aromatic solvents, with and without the nucleophile benzylmercaptan present, led to isolation of both radical-trapping arene adducts and nucleophilic capture benzyl thioether products. On the basis of these product distribution studies, the intermediacies of, first, a cyclopentenyl radical and, next, an orthoquinonemethide electrophile are postulated.
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U2 - 10.1021/ja0642616
DO - 10.1021/ja0642616
M3 - Article
C2 - 16984207
AN - SCOPUS:33749174128
SN - 0002-7863
VL - 128
SP - 12562
EP - 12573
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 38
ER -